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B
=
A0
n
A0
- n
A
X
A
=
n
A0
B0
n
B0
- n
B
X
B
=
n
B0
Extent of Reaction
Stoichiometric coefficient
Stoichiometry
Stoichiometry
Please find the stoichiometric coefficients, extent of reaction
conversion, yield with respect to methane, and selectivity.
t =0 5 15 0.2 3
t 0 1 3.5
0
CH
4
+ H
2
O CO + H
2
C + H
2
3
Energy Balances
Conservation of Energy (First Law of Thermodynamics)
Energy Balances
Work Terms
Compressor
Stirrer
Pump
0
Energy Balances
Energy Terms
Internal Energy Potential Energy
Kinetic Energy
Magnetic and Electrical Energies
Energy Balances
Energy Balances
Batch Reactor
Energy Balances
General Energy Balance Equation for Batch Reactor
Heat of Reaction
Sensible Heat
Expansion term
Latent Heat
Energy Balances
General Energy Balance Equation for Batch Reactor
Heat of Reaction
Sensible Heat
Expansion term
Latent Heat
Energy Balances
Heat of Reactions
Heat associated breaking and forming of chemical bonds in a
molecule
Energy Balances
Standard Heat of Formation (H
f
o
)
C(s) +O
2
(g, STP) CO
2
(g, STP)
The change in enthalpy associated with any chemical reaction that involves the
creation of a molecule from elements in their standard state is called the heat of
formation.
+
C
O O
CO
2
Energy Balances
Standard Heat of Formation
Energy Balances
Standard Heat of Combustion
Energy Balances
Constant Pressure
Energy Balances
Constant Volume (Ideal Gas)
(2.1) Derive the above equation from the general energy balance equation
for a batch reactor.
Energy Balances
Constant Volume vs Constant Pressure
Energy Balances
Liquid phase batch reactor 1
The exothermic elementary liquid phase reaction:
was carried out in a batch reactor with a cooling coil to keep the reactor
isothermal at 27C. The reactor was filled with 2 mol/L of reactant A.
(a) How long does it take to reach 95 % conversion?
(b) What is the total amount of heat (kcal) removed by the cooling coil
when this conversion is reached?
(c) What is the maximum rate by which the heat must be removed by
the heating coil (kcal/min) and at what time does this maximum occurs?
(d) What is the adiabatic temperature rise for this reactor and its
significance?
Energy Balances
Additional information:
Liquid phase batch reactor 2
(2.2) Repeat the calculation for a second order irreversible reaction:
Energy Balances
First Order Reaction Kinetics
0
0.5
1
1.5
2
0 100 200 300 400
time (s)
C
A
(
M
)
0
0.2
0.4
0.6
0.8
1
0 100 200 300 400
time (s)
C
o
n
v
e
r
s
i
o
n
(
X
)
Energy Balances
Heat Removal by Cooling Coil
400
0
100
200
300
400
500
0 100 200 300
time (s)
-
Q
(
k
c
a
l
/
s
)
0
10000
20000
30000
0 100 200 300 400
time (s)
-
Q
(
k
c
a
l
)
.
Energy Balances
Adiabatic Heating and Temperature Rise
.
0
100
200
300
0 2 4 6 8 10 12 14
time (min)
T
e
m
p
e
r
a
t
u
r
e
(
C
)
Ea =5 kcal/mol
10 20
0
50
100
150
200
250
0 0.2 0.4 0.6 0.8 1
Conversion (X)
T
(
K
)
Energy Balances
Runaway Reaction
.
Ea =5 kcal/mol
10 20
0
0.2
0.4
0.6
0.8
1
0 50 100 150 200 250
time (min)
C
o
n
v
e
r
s
i
o
n
(
X
)
Isothermal
0
0.2
0.4
0.6
0.8
1
0 2 4 6 8 10 12 14
time (min)
C
o
n
v
e
r
s
i
o
n
(
X
)
Thermodynamics
Why study chemical reaction equilibrium when operating reactors
are never at chemical equilibrium?
Chemical Reaction Equilibrium
(1) Determine the limits of reactor performance,
(2) Explore possible design and operation changes that overcomes
these restriction and optimizes reactor performance.
Thermodynamics
Gibbs Energy (G)
Physical and Chemical Precondition for Biochemical Reactions
including Cell Metabolism and Enzymatic Catalysis
UNCATALYZED ENZYMATICALLY CATALYZED
Thermodynamics
G <0 Spontaneous, Energy releasing process Exergonic Process
G =0 Equilibrium process
G >0 Non-spontaneous, Energy consuming process Endergonic Process
Energy (Photon, Heat)
Nutrient (Reduced molecules)
cell
metabolism
STORED
ENERGY
http://www.biologie.uni-hamburg.de/b-online/e18/18.htm
Thermodynamics
Work by using exergonic processes to drive endergonic processes
Cell Metabolism
ATP is an important source of energy
Thermodynamics
Reaction Equilibrium is harnessed in microelectronic fabrications
Semiconductor Processing
Chemical Vapor Deposition
Thermodynamics
Chemical Vapor Deposition
Thermodynamics
Reaction Equilibrium is harnessed in microelectronic fabrications
Chemical Vapor Deposition and Etching
Thermodynamics
Thermodynamic System
The Gibbs free energy of the system (G) is the convenient energy
function of these state variables.
The equilibrium state of the system is completely
defined once the temperature, pressure and moles
of each components are specified.
Thermodynamics
Condition for Reaction Equilibrium
The Gibbs free energy:
Extend of Reaction
Thermodynamics
Condition for Reaction Equilibrium
The Gibbs free energy:
Extend of Reaction
Thermodynamics
Condition for Reaction Equilibrium
Necessary condition for
reaction equilibrium
Standard Gibbs energy
activity fugacity
Thermodynamics
Condition for Reaction Equilibrium
The Gibbs free energy for a reaction system:
Standard Gibbs energy
of change
Equilibrium
constant
Thermodynamics
Ideal Gas Equilibrium 1
High octane fuel additives are produced by reaction of isobutanewith
1-butenehydrocarbons:
Determine the equilibrium composition of the reaction mixture at a
pressure of 2.5 atm and temperature of 400 K. The standard Gibbs
energy change for this reaction at 400 K is 3.72 kcal/mol.
Assume that equimolar amounts of isobutane and 1-butene are present
in the initial mixture.
(2.3) Please repeat the calculation if the initial ratio of I/B =100, 10, 0.1.
Thermodynamics
Modified Gibbs Energy
Single
reaction
Thermodynamics
Modified Gibbs Energy
=0.469